Solid state forms of cyantraniliprole and uses thereof

Abstract

The present invention relates to new solid forms of Cyantraniliprole, processes for preparation thereof, uses thereof and agrochemical compositions thereof.

Description

SOLID STATE FORMS OF CYANTRANILIPROLE AND USES THEREOFTechnical Field

[0001] The present disclosure relates to new solid forms of Cyantraniliprole, processes for preparation thereof and agrochemical compositions thereof. This invention is also directed to processes for preparation of a crystalline form of Cyantraniliprole from the said new forms of Cyantraniliprole.Background of the Disclosure

[0002] The control of invertebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. Certain anthranilamides, their N-oxides, salts and compositions suitable for agronomic and non-agronomic uses, and a method of their use for controlling invertebrate pests in both agronomic and non-agronomic environments. The control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important.

[0003] Cyantraniliprole is an anthranilamide insecticide of the ryanoid class. It is a systemic diamide insecticide used specifically to control lepidopteran pests in agriculture. It is a promising insecticide due to its unique mode of action in activating muscle ryanodine receptors, causing contraction and paralysis of some pests. It has already been registered for use against lepidopterous pests and aphids on several fruits and vegetables including apples, peaches, tomatoes, watermelons, and cucumbers.

[0004] Cyantraniliprole has the chemical name, 3-Bromo-l-(3-chloro-2-pyridinyl)-N- [4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-lH-pyrazole-5-carboxamide.

[0005] Cyantraniliprole has the following chemical structure:

[0006] Cyantraniliprole, an N-oxide or a salt, and process thereof, was first disclosed by E.I. du Pont Company in the International publication, WO 2004 / 067528. Further processes for its preparation were disclosed in WO 2006 / 062978 and WO 2010 / 056720.The purification process of Cyantraniliprole is disclosed in W02006 / 062978 by recrystallization of crude from 1 -propanol.

[0007] Furthermore, methods were disclosed in the WO2010056720 publication for the preparation of a non-hydratable polymorph A of Cyantraniliprole from a hydratable polymorph B of Cyantraniliprole. More specifically, WO2010056720 publication is directed to a method for preparing Polymorph A of Cyantraniliprole comprising heating at a temperature between about 40°C and the boiling point of the solvent a mixture comprising a solvent selected from the group consisting of water, n-heptane, 1 -chlorobutane, toluene, 1 -butanol and 1 -pentanol, and Polymorph B of Cyantraniliprole. The disadvantage of this process of for preparing Polymorph A of Cyantraniliprole in the WO2010056720 publication is that it requires heating and / or seeding. There is thus a need for a process for preparing Polymorph A of Cyantraniliprole, which does not require any heating or any kind of seeding.

[0008] Furthermore, WO2021 / 249395 publication also discloses other crystalline forms of Cyantraniliprole, such as Form C, Form D and Form F, and processes for preparation thereof.

[0009] Polymorphism, the occurrence of different crystal forms, is a property of some molecules and molecular complexes. A single compound, like Cyantraniliprole, may give rise to a variety of polymorphs having distinct crystal structures and physical properties like melting point, thermal behaviours (e.g. measured by thermogravimetric analysis - "TGA", or differential scanning calorimetry - "DSC"), X-ray powder diffraction (XRPD) pattern, infrared absorption fingerprint, Raman absorption fingerprint, and solid state (13C-) NMR spectrum. One or more of these techniques may be used to distinguish different polymorphic forms of a compound.

[0010] Different salts and solid state forms (including solvated forms) of an active ingredient may possess different properties. Such variations in the properties of different salts and solid state forms and solvates may provide a basis for improving formulation, for example, by facilitating better processing or handling characteristics, improving the dissolution profile, or improving stability (polymorph as well as chemical stability) and shelf-life. These variations in the properties of different salts and solid state forms may also provide improvements to the final formulation or recipe, for instance, if they serve to improve dissolution. Different salts and solid state forms and solvates of an active ingredient may also give rise to a variety of polymorphs or crystalline forms, which may in turn provide additional opportunities to use variations in the properties and characteristics of a solid active ingredient for providing an improved product.

[0011] Inventing new salts, solid state forms and solvates of an agrochemical product can provide materials having desirable processing properties, such as ease of handling, ease of processing, storage stability, and ease of purification or as desirable intermediate crystal forms that facilitate conversion to other salts or polymorphic forms. New salts, polymorphic forms and solvates of an active ingredient can also provide an opportunity to improve the performance characteristics of an agrochemical product (dissolution profile, permeability, etc.). It expands the range of materials that an expert in the field can avail for formulation optimization, for example by providing a product with different properties, e.g., a different crystal habit, higher crystallinity or polymorphic stability which may offer better processing or handling characteristics, improved dissolution profile, or improved shelf-life.

[0012] Finding new solid state forms and solvates also help preparation of other forms of an active ingredient. Inter-convertibility of one form of an active ingredient to another form opens new useful options in the art.

[0013] For at least these reasons, there is a need for some novel solid state forms (including solvated forms or salts) of Cyantraniliprole.Summary

[0014] The present disclosure relates to new solid state forms of Cyantraniliprole, processes for preparation thereof, and agrochemical compositions including this solid state form.

[0015] This present disclosure is also directed to processes for preparation of a crystalline form of Cyantraniliprole from the said new forms of Cyantraniliprole.

[0016] The present disclosure also provides use of one solid state form of Cyantraniliprole for preparing other solid state forms of Cyantraniliprole, Cyantraniliprole N- oxide and solid state forms of a Cyantraniliprole salt.

[0017] In an embodiment, the present disclosure provides use of Cyantraniliprole Form O for preparing Form A of Cyantraniliprole.

[0018] In another embodiment, the present disclosure provides use of CyantraniliproleForm W for preparing Form A of Cyantraniliprole.

[0019] In another embodiment, the present disclosure provides use of CyantraniliproleForm Z for preparing Form A of Cyantraniliprole.

[0020] The present disclosure also provides solid state form of Cyantraniliprole for uses in the preparation of other solid state forms of Cyantraniliprole, Cyantraniliprole N-oxide and solid state forms of a Cyantraniliprole salts.

[0021] In one embodiment, the present disclosure encompasses the described solid state forms of Cyantraniliprole for use in the preparation of agrochemical compositions and / or formulations, optionally for agronomic and non-agronomic uses, and a method of their use for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0022] In another embodiment, the present disclosure encompasses uses of the described solid state forms of Cyantraniliprole for the preparation of agrochemical compositions and / or formulations.

[0023] The present disclosure further provides agrochemical compositions including one or more solid state forms of Cyantraniliprole according to the present disclosure.

[0024] In yet another embodiment, the present disclosure encompasses agrochemical formulations including one or more of the described solid state forms of Cyantraniliprole and at least one additional component selected from the group consisting of a surfactant, a solid diluent and liquid diluent and optionally an effective amount of at least one additional biologically active compound or agent.

[0025] The present disclosure encompasses processes to prepare said agrochemical formulations of Cyantraniliprole including one or more of the described solid state forms and at least one additional component selected from the group consisting of a surfactant, a solid diluent and liquid diluent and optionally an effective amount of at least one additional biologically active compound or agent.

[0026] The solid state forms defined herein as well as the agrochemical compositions or formulations of the solid state forms of Cyantraniliprole can be used as systemic diamide insecticide for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0027] The present disclosure also provides methods for controlling invertebrate pests comprising applying solid state forms of Cyantraniliprole by activating muscle ryanodine receptors, causing contraction and paralysis of some pests.

[0028] The present disclosure also provides uses of the solid state forms of Cyantraniliprole of the present disclosure, or at least one of the above agrochemical compositions or formulations for controlling invertebrate pests in both agronomic and non- agronomic environments.Brief Description of the Figures

[0029] Figure 1 shows an X-ray powder diffractogram (XRPD) of Form O of Cyantraniliprole.

[0030] Figure 2 shows an X-ray powder diffractogram (XRPD) of Form W of Cyantraniliprole.

[0031] Figure 3 shows an X-ray powder diffractogram (XRPD) of Form Z of Cyantraniliprole.Detailed Description

[0032] The present disclosure relates to solid state forms of Cyantraniliprole, processes for preparation thereof and agrochemical compositions including the solid state form. The disclosure also relates to the conversion of the described solid state form of Cyantraniliprole to other solid state forms of Cyantraniliprole, Cyantraniliprole N-oxide, Cyantraniliprole salts and their solid state forms thereof.

[0033] The solid state forms of Cyantraniliprole according to the present disclosure may have advantageous properties selected from at least one of: chemical or polymorphic purity, flowability, solubility, dissolution rate, morphology or crystal habit, stability - such as chemical stability as well as thermal and mechanical stability with respect to polymorphic conversion, stability towards dehydration and / or storage stability, a lower degree of hygroscopicity, low content of residual solvents and advantageous processing and handling characteristics such as compressibility, or bulk density.

[0034] A crystal form may be referred to herein as being characterized by graphical data as depicted in a Figure. Such data include, for example, powder X-ray diffractograms and solid state NMR spectra. As is well-known in the art, the graphical data potentially provides additional technical information to further define the respective solid state form which can not necessarily be described by reference to numerical values or peak positions alone. In any event, the skilled person will understand that such graphical representations of data may be subject to small variations, e.g., in peak relative intensities and peak positions due to factors such as variations in instrument response and variations in sample concentration and purity, which are well known to the skilled person. Nonetheless, the skilled person would readily be capable of comparing the graphical data in the Figures herein with graphical data generated for an unknown crystal form and confirm whether the two sets of graphical data are characterizing the same crystal form or two different crystal forms. A crystal form of Cyantraniliprole referred to herein as being characterized by graphical data "as depicted in" a Figure will thus be understood to include any crystal form of Cyantraniliprole, characterized with the graphical data having such small variations, as are well known to the skilled person, in comparison with the Figure.

[0035] A pure solid state form (or polymorph) may be referred to herein as polymorphically pure or as substantially free of any other solid state (or polymorphic) forms. As used herein in this context, the expression "substantially free of any other forms" will be understood to mean that the solid state form contains about 20% or less, about 10% or less, about 5% or less, about 2% or less, about 1% or less, or 0% of any other forms of the subject compound as measured, for example, by XRPD. Thus, the solid state form of Cyantraniliprole described herein as substantially free of any other solid state forms would be understood to contain greater than about 80% (w / w), greater than about 90% (w / w), greater than about 95% (w / w), greater than about 98% (w / w), greater than about 99% (w / w), or 100% of the subject solid state form of Cyantraniliprole. Accordingly, in some embodiments of the disclosure, the described solid state form of Cyantraniliprole may contain from about 1% to about 20% (w / w), from about 5% to about 20% (w / w), or from about 5% to about 10% (w / w) of one or more other solid state forms of the same Cyantraniliprole.

[0036] In an aspect the present disclosure contemplates that a certain solid state form of Cyantraniliprole can exist in the presence of any other of the solid state forms or mixture thereof. Accordingly, in one embodiment, the present disclosure provides form A, for example, wherein form A is present in a solid form that includes less than 95%, less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, less than 3% or less than 1% by weight of any other physical forms of Cyantraniliprole.

[0037] The solid state forms of Cyantraniliprole as characterized herein may be present also in traces in an agrochemical compositions or formulations for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0038] As used herein, unless stated otherwise, XRPD peaks reported herein are optionally measured using CuKa, radiation, = 1.54187 A.

[0039] As used herein, the term "isolated" in reference to solid state forms of Cyantraniliprole of the present disclosure corresponds to solid state form of Cyantraniliprole that is physically separated from the reaction mixture in which it is formed.

[0040] A thing, e.g., a reaction mixture, may be characterized herein as being at, or allowed to come to "room temperature", often abbreviated "RT." This means that the temperature of the thing is close to, or the same as, that of the space, e.g., the room or fume hood, in which the thing is located. Typically, room temperature is from about 20°C to about 30°C, about 22°C to about 27°C, or about 25°C.

[0041] A process or step may be referred to herein as being carried out "overnight." This refers to a time interval, e.g., for the process or step, that spans the time during the night, when that process or step may not be actively observed. This time interval is from about 8 to about 20 hours, about 10 to about 18 hours, or about 16 hours.

[0042] The amount of solvent employed in a chemical process, e.g., a reaction or crystallization, may be referred to herein as a number of "volumes" or "vol" or "V." For example, a material may be referred to as being suspended in 10 volumes (or 10 vol or 10V) of a solvent. In this context, this expression would be understood to mean milliliters of the solvent per gram of the material being suspended, such that suspending a 5 grams of a material in 10 volumes of a solvent means that the solvent is used in an amount of 10 milliliters of the solvent per gram of the material that is being suspended or, in this example, 50 mL of the solvent. In another context, the term "v / v" may be used to indicate the number of volumes of a solvent that are added to a liquid mixture based on the volume of that mixture. For example, adding methyl tert-butyl ether (MTBE) (1.5 v / v) to a 100 ml reaction mixture would indicate that 150 mL of MTBE was added.

[0043] As used herein, the term "reduced pressure" refers to a pressure of about 10 mb ar to about 50 mb ar.

[0044] The present disclosure includes a solid state form of Cyantraniliprole designated as Form O. The Form O of Cyantraniliprole can be characterized by data selected from one or more of the following: an XRPD pattern having peaks at 7.5, 8.3, 13.1, 14.9 and 21.1 degrees 2-theta ± 0.2 degrees 2-theta; an XRPD pattern as depicted in Figure 1; and combinations of these data.

[0045] Crystalline Form O of Cyantraniliprole may be further characterized by the XRPD pattern having peaks at 7.5, 8.3, 13.1, 14.9 and 21.1 degrees 2-theta ± 0.2 degrees 2- theta, and also having one, two or three additional peaks selected from 18.5, 19.5, 19.8, 20.2 and 24.1 degrees 2- theta ± 0.2 degrees 2-theta.

[0046] Crystalline Form O of Cyantraniliprole may be characterized by any combination of at least four peaks in an XRPD pattern as depicted in Figure 1.

[0047] In an embodiment, the crystalline form O of Cyantraniliprole is a 1,4-di oxane solvate.

[0048] The present disclosure also includes a solid state form of Cyantraniliprole designated as Form W. The Form W of Cyantraniliprole can be characterized by data selected from one or more of the following: an XRPD pattern having peaks at 6.6, 9.7, 17.6, 20.2 and21.1 degrees 2-theta ± 0.2 degrees 2-theta; an XRPD pattern as depicted in Figure 2; and combinations of these data.

[0049] Crystalline Form W of Cyantraniliprole may be further characterized by the XRPD pattern having peaks at 6.6, 9.7, 17.6, 20.2 and 21.1 degrees 2-theta ± 0.2 degrees 2- theta, and also having one, two or three additional peaks selected from 10.7, 14.9, 15.8, 18.6 and 27.1 degrees 2- theta ± 0.2 degrees 2-theta.

[0050] Crystalline Form W of Cyantraniliprole may be characterized by any combination of at least four peaks in an XRPD pattern as depicted in Figure 2.

[0051] In an embodiment, the crystalline form W of Cyantraniliprole is a solvate.

[0052] The present disclosure further includes a solid state form of Cyantraniliprole designated as Form Z. The Form Z of Cyantraniliprole can be characterized by data selected from one or more of the following: an XRPD pattern having peaks at 8.6, 9.0, 15.6, 17.2 and 23.0 degrees 2-theta ± 0.2 degrees 2-theta; an XRPD pattern as depicted in Figure 3; and combinations of these data.

[0053] Crystalline Form Z of Cyantraniliprole may be further characterized by the XRPD pattern having peaks at 8.6, 9.0, 15.6, 17.2 and 23.0 degrees 2-theta ± 0.2 degrees 2- theta, and also having one, two or three additional peaks selected from 10.5, 11.3, 19.3, 20.2, 21.1 and 24.1 degrees 2- theta ± 0.2 degrees 2-theta.

[0054] Crystalline Form Z of Cyantraniliprole may be characterized by any combination of at least four peaks in an XRPD pattern as depicted in Figure 3.

[0055] In an embodiment, the crystalline form Z of Cyantraniliprole is anhydrous.

[0056] In a further embodiment, the present disclosure provides a process for preparation of crystalline form O of Cyantraniliprole comprising slurring form B of Cyantraniliprole with 1,4-Dioxane, followed by filtering and drying.

[0057] In an embodiment, the present disclosure provides a process for preparation of crystalline form W of Cyantraniliprole comprising dissolving form B of Cyantraniliprole in a chlorinated hydrocarbon solvent, mixing with an aliphatic hydrocarbon solvent, followed by stirring, filtering, and drying.

[0058] In a specific embodiment, the present disclosure provides a process for preparation of crystalline form W of Cyantraniliprole comprising dissolving form B of Cyantraniliprole in dichloromethane, mixing with n-heptane, followed by stirring, filtering, and drying.

[0059] In an embodiment, the present disclosure provides a process for preparation of crystalline form Z of Cyantraniliprole comprising heating form F of Cyantraniliprole in high temperature overnight.

[0060] In an embodiment, the present disclosure provides a process for preparation of crystalline form A of Cyantraniliprole comprising starting from a form O of Cyantraniliprole, which is slurried with a suitable solvent selected from 1 -propanol, 1 -butanol, n-heptane, methyl cyclohexane, isoamyl alcohol, isobutanol, 1 -pentanol, 2-butanol, isobutyl acetate, isobutyric acid, isopropanol, followed by decanting.

[0061] In a further embodiment, the present disclosure provides a process for preparation of crystalline form A of Cyantraniliprole comprising starting from a form W of Cyantraniliprole, which is slurried with a suitable solvent selected from 1 -propanol, 1 -butanol, 1 -pentanol, n-heptane, methyl cyclohexane, isoamyl alcohol, isobutanol, 2-butanol, isobutyl acetate, isobutyric acid, isopropanol, followed by decanting.

[0062] In a further embodiment, the present disclosure provides a process for preparation of crystalline form A of Cyantraniliprole comprising starting from a form F of Cyantraniliprole, which is slurried with a suitable solvent selected from 1 -propanol, 1 -butanol, 1 -entanol, n-heptane, methyl cyclohexane, isoamyl alcohol, isobutanol, 1 -pentanol, 2-butanol, isobutyl acetate, isobutyric acid, isopropanol, followed by decanting.

[0063] In a further embodiment, the present disclosure provides a process for preparation of crystalline form A of Cyantraniliprole comprising starting from amorphous form of Cyantraniliprole, which is slurried with a suitable solvent selected from 1 -propanol, 1- butanol, 1 -entanol, n-heptane, methyl cyclohexane, isoamyl alcohol, isobutanol, 1 -pentanol, 2- butanol, isobutyl acetate, isobutyric acid, isopropanol, followed by decanting.

[0064] In a specific embodiment, the present disclosure provides a process for preparation of pure crystalline form A of Cyantraniliprole comprising starting from a form of Cyantraniliprole selected from a group comprising form O, form W, form F and amorphous.

[0065] In a more specific embodiment, the present disclosure provides a process for preparation of pure crystalline form A of Cyantraniliprole comprising starting from form W.

[0066] In an embodiment, the present disclosure provides a process for preparation of amorphous Cyantraniliprole comprising dissolving form A of Cyantraniliprole in a chlorinated hydrocarbon solvent, mixing with an aliphatic hydrocarbon solvent, followed by stirring, filtering, and drying.

[0067] In a specific embodiment, the present disclosure provides a process for preparation of amorphous Cyantraniliprole comprising dissolving form A of Cyantraniliprole in 1,1,2,2-tetrachloroethane, mixing with n-heptane, followed by stirring, filtering, and drying.

[0068] In an embodiment, the present disclosure provides a process for preparation of form F of Cyantraniliprole comprising slurring form O of Cyantraniliprole with an aromatic solvent, followed by filtering and drying.

[0069] In a specific embodiment, the present disclosure provides a process for preparation of form F of Cyantraniliprole comprising slurring form O of Cyantraniliprole with toluene, followed by filtering and drying.

[0070] The present disclosure also provides the solid state forms of Cyantraniliprole of the present disclosure for use in the preparation of other solid state forms of Cyantraniliprole, Cyantraniliprole N-oxide, Cyantraniliprole salts and solid state forms thereof.

[0071] In another embodiment, the present disclosure encompasses the above described solid state forms of Cyantraniliprole for use in the preparation of agrochemical compositions and / or formulations, optionally for agronomic and non-agronomic uses, and a method of their use for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0072] In another embodiment, the present disclosure encompasses the use of the described solid state form of Cyantraniliprole for the preparation of agrochemical compositions and / or formulations.

[0073] The present disclosure further provides agrochemical compositions including one or more solid state forms of Cyantraniliprole according to the present disclosure.

[0074] In yet another embodiment, the present disclosure encompasses agrochemical formulations including one or more of the described solid state forms of Cyantraniliprole and at least one additional component selected from the group consisting of a surfactant, a solid diluent and liquid diluent and optionally an effective amount of at least one additional biologically active compound or agent.

[0075] In an embodiment, the present disclosure encompasses processes to prepare said agrochemical formulations of Cyantraniliprole including one or more of the described solid state forms and at least one additional component selected from the group consisting of a surfactant, a solid diluent and liquid diluent and optionally an effective amount of at least one additional biologically active compound or agent.

[0076] In one embodiment, the solid state forms defined herein as well as the agrochemical compositions or formulations of the solid state forms of Cyantraniliprole can beused as systemic diamide insecticide for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0077] In further embodiment, the present disclosure also encompasses methods for controlling invertebrate pests comprising applying solid state forms of Cyantraniliprole by activating muscle ryanodine receptors, causing contraction and paralysis of some pests.

[0078] In yet another embodiment, the present disclosure also covers uses of the solid state forms of Cyantraniliprole of the present disclosure, or at least one of the above agrochemical compositions or formulations for controlling invertebrate pests in both agronomic and non-agronomic environments.

[0079] Having described the disclosure with reference to certain preferred embodiments, other embodiments will become apparent to one skilled in the art from consideration of the specification. The disclosure is further illustrated by reference to the following examples describing in detail the preparation of the solid forms and methods of use of the disclosure. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the disclosure.Analytical MethodsX-ray powder diffraction method:

[0080] Powder X-ray Diffraction was performed on an X-Ray powder diffractometer, PANalytical AERIS, operating with CuKa, radiation, ( = 1.54060 A-); zero background sample holders.Measurement parameters:Scan range: 3-45 degrees 2-thetaOverall scan speed 0.16098%Sample holder: Zero background silicon platePrior to analysis, the samples were gently ground using a mortar and pestle to obtain a fine powder. Optionally, silicon powder can be added in a suitable amount as internal standard in order to calibrate the positions of the diffractions. The ground sample was adjusted into a cavity of the sample holder and the surface of the sample was smoothed using a cover.Examples

[0081] Solid forms of Cyantraniliprole were prepared according to the following procedures:

[0082] The starting materials for the preparation of the solid forms of the present invention were prepared following the prior art procedures. For example, Form B and Form A of Cyantraniliprole can be obtained by procedures published in WO 2006 / 062978 and also in WO 2010 / 056720. Form F of Cyantraniliprole is disclosed by XRPD data in WO2021 / 249395 publication. Form F of Cyantraniliprole can also be prepared according to WO2021 / 249395 or the procedures as described hereunder. The XRPD data of Form B and Form A are disclosed in WO 2010 / 056720.New solid crystalline forms of Cyantraniliprole were prepared according to following preparatory examples:Example 1: Preparation of form O of Cyantraniliprole:

[0083] 15g of form B of Cyantraniliprole was weighted in a 250 mL glass bottle and150 mL of 1,4-Dioxane was added in it. The solution, thereafter, was kept on the magnetic stirrer for room temperature slurry (for 18 hrs at 750 rpm). After 18 hrs, the solution was filtered through Whatman filter paper and the wet sample was subjected (decanting out the supernatant part) to XRPD study corroborating formation of form O. Next, the sample was placed in vacuum dry for 3 hrs (at RT, 760 mm of Hg) and taken its XRPD suggesting retention of form O after drying.Example 1A: Preparation of form O of Cyantraniliprole (alternative method):

[0084] 150g of form B of Cyantraniliprole was stirred in 1500ml 1,4-di oxane over the weekend at rt, filtered and air dried. Solid was then gently ground with spatula and analysed by XRD.Example 2: Preparation of form W of Cyantraniliprole:

[0085] 1g of form B of Cyantraniliprole was taken into a 2L glass bottle along with a large sized magnetic bead (size: 2 inch). 300 mL of DCM was added into it and kept the mixture on a magnetic stirrer to stir for ~1 hr (at RT, 650 rpm) until getting a clear solution. After the compound fully dissolved in DCM, 800 mL of n-Heptane was added as fast as possible and left the solution to stir for another 4-5 minutes at the same reaction condition. After that, the solution was filtered through Whatman (125 mm) filter paper. The off-white color wet compound was subjected to XRPD what corroborates formation of Form W. After that, the wet powder compound was placed in vacuum oven to dry at RT for ~3 hrs. and its XRPD is taken suggesting retention of form W after drying.Example 3: Preparation of form Z of Cyantraniliprole:

[0086] 124 g sample of wet form F (obtained by crystallization in toluene, followed by filtering, but not drying) of Cyantraniliprole was heated overnight at 150°C. After that, the sample was subjected to XRPD analysis.Known solid crystalline form A of Cyantraniliprole were prepared from other forms of Cyantraniliprole according to following preparatory examples:Example 4: Preparation of Cyantraniliprole Form A from Form F

[0087] A sample of form F of Cyantraniliprole was taken in 7 mL glass vial individually and the following solvents were added into the vials and the slurry was kept on magnetic stirrer at RT slurry (at 750 rpm) according to the following parameters. After that, the solution was centrifuged at 7000 rpm (2x5 mins) and subjected (decanting out the supernatant part) to XRPD study confirming the formation of form A in each case.*Pure form A of Cyantraniliprole is obtained following given conditionsExample 5: Preparation of Cyantraniliprole Form A from Form O

[0088] A sample of form O was taken in 7 mL glass vial individually and the following solvents were added into the vials and the slurry was kept on magnetic stirrer at RT slurry (at 750 rpm) according to the following parameters. After that, the solution was centrifuged at 7000 rpm (2x5 mins) and subjected (decanting out the supernatant part) to XRPD study confirming the formation of form A in each case.*Pure form A of Cyantraniliprole is obtained following given conditionsExample 6: Preparation of Cyantraniliprole Form A from Form W

[0089] A sample of form W was taken in 7 mL glass vial individually and the following solvents were added into the vials and the slurry was kept on magnetic stirrer at RT slurry (at 750 rpm) according to the following parameters. After that, the solution was centrifuged at 7000 rpm (2x5 mins) and subjected (decanting out the supernatant part) to XRPD study confirming the formation of form A in each case.In all the instances in the above table form A of Cyantraniliprole is obtained in pure form.Example 7: Preparation of Cyantraniliprole Form A from slurry of amorphous

[0090] A sample of amorphous was taken in 7 mL glass vial individually and the following solvents were added into the vials and the slurry was kept on magnetic stirrer at RT slurry (at 750 rpm) according to the following parameters. After that, the solution was centrifuged at 7000 rpm (2x5 mins) and subjected (decanting out the supernatant part) to XRPD study confirming the formation of form A in each case.*Pure form A of Cyantraniliprole is obtained following given conditionsThe processes described above in Example 4-7 also lead to pure from A. Purity is defined as no detection of additional peaks in the X-Ray powder diffractometer. In quantitative terms this corresponds to about 98% form A.

[0091] Moreover, amorphous form and solid crystalline form F of Cyantraniliprole were prepared from other forms of Cyantraniliprole according to following preparatory examples:Example 8: Preparation of amorphous form of Cyantraniliprole

[0092] 2 g of Cyantraniliprole Form A was weighed and placed in a 100 mL glass bottle. 30 mL of 1,1,2,2-Tetrachloroethane was added and the resultant mixture was stirred at 25 °C (with 800 rpm) until getting a clear solution. 16 mL of n-heptane was added dropwise into the clear solution until the precipitation is observed. The resultant suspension is slurriedat 25 °C (with 800 rpm) for 20 minutes and the white color suspension is filtered through Whatman (125 mm) filter paper. The obtained solid is dried under vacuum at 25 °C (-760 mm of Hg) for 18 hours and PXRD data is collected.Example 9: Preparation of form F of Cyantraniliprole

[0093] 3.4 g of Form O of Cyantraniliprole is weighed and placed in a 100 mL glass bottle. 34 mL of toluene was added and the resultant mixture is slurried at 25 °C for 18 hours (with 800 rpm). The suspension is filtered through Whatman (125 mm) filter paper and PXRD data of the wet sample is collected to confirm it to be form F.

Claims

CLAIMS:

1. A crystalline form O of Cyantraniliprole, which is characterized by data selected from one or more of the following:

1. an XRPD pattern having peaks at 7.5, 8.3, 13.1, 14.9 and 21.1 degrees 2- theta ± 0.2 degrees 2-theta; ii. an XRPD pattern as depicted in Figure 1.

2. The crystalline form of Cyantraniliprole according to claim 1, which is characterized by an XRPD pattern having peaks at 7.5, 8.3, 13.1, 14.9 and 21.1 degrees 2-theta ± 0.2 degrees 2- theta, and also having one, two or three additional peaks selected from 18.5, 19.5, 19.8, 20.2 and 24.1 degrees 2-theta ± 0.2 degrees 2-theta.

3. The crystalline form of Cyantraniliprole according to claim 1 is a 1,4-di oxane solvate.

4. A crystalline form W of Cyantraniliprole, which is characterized by data selected from one or more of the following: i. an XRPD pattern having peaks at 6.6, 9.7, 17.6, 20.2 and 21.1 degrees 2- theta ± 0.2 degrees 2-theta; ii. an XRPD pattern as depicted in Figure 2.

5. The crystalline form of Cyantraniliprole according to claim 4, which is characterized by an XRPD pattern having peaks at 6.6, 9.7, 17.6, 20.2 and 21.1 degrees 2-theta ± 0.2 degrees 2- theta, and also having one, two or three additional peaks selected from 10.7, 14.9, 15.8, 18.6 and 27.1 degrees 2-theta ± 0.2 degrees 2-theta.

6. The crystalline form of Cyantraniliprole according to claim 4 is a solvate.

7. A crystalline form Z of Cyantraniliprole, which is characterized by data selected from one or more of the following: i. an XRPD pattern having peaks at 8.6, 9.0, 15.6, 17.2 and 23.0 degrees 2- theta ± 0.2 degrees 2-theta; ii. an XRPD pattern as depicted in Figure 3.

8. The crystalline form of Cyantraniliprole according to claim 7, which is characterized by an XRPD pattern having peaks at 8.6, 9.0, 15.6, 17.2 and 23.0 degrees 2-theta ± 0.2 degrees 2- theta, and also having one, two or three additional peaks selected from 10.5, 11.3, 19.3, 20.2, 21.1 and 24.1 degrees 2-theta ± 0.2 degrees 2-theta.

9. The crystalline form of Cyantraniliprole according to claim 7 is anhydrous.

10. A process for preparation of crystalline form O of Cyantraniliprole according to claim 1 comprising slurring form B of Cyantraniliprole with 1,4-Dioxane, followed by filtering and drying.

11. A process for preparation of crystalline form W of Cyantraniliprole according to claim 4 comprising dissolving form B of Cyantraniliprole in a chlorinated hydrocarbon solvent, mixing with an aliphatic hydrocarbon solvent, followed by stirring, filtering, and drying.

12. The process according to claim 11, wherein the chlorinated hydrocarbon solvent is dichloromethane, and the aliphatic hydrocarbon solvent is n-heptane.

13. A process for preparation of crystalline form Z of Cyantraniliprole according to claim 7 comprising heating form F of Cyantraniliprole in high temperature overnight.

14. A process for preparation of crystalline form A of Cyantraniliprole comprising starting from a form of Cyantraniliprole, which is slurried with a suitable solvent selected from 1- propanol, 1 -butanol, 1 -pentanol, n-heptane, methyl cyclohexane, isoamyl alcohol, isobutanol, 2-butanol, isobutyl acetate, isobutyric acid, isopropanol.

15. The process according to claim 14, wherein the starting form of Cyantraniliprole is a form selected from a group comprising form O, form W, form F and amorphous.

16. The process according to any of claim 14 and claim 15 wherein the crystalline form A of Cyantraniliprole is a pure form A, which is prepared starting from a form of Cyantraniliprole selected from a group comprising form O, form W, form F and amorphous.

17. The process according to claim 16, wherein the starting form of Cyantraniliprole is form W.

18. A process for preparation of amorphous Cyantraniliprole comprising dissolving form A of Cyantraniliprole in a chlorinated hydrocarbon solvent, mixing with an aliphatic hydrocarbon solvent, followed by stirring, filtering, and drying.

19. The process according to claim 18, wherein the chlorinated hydrocarbon solvent is 1,1,2,2-tetrachloroethane, and the aliphatic hydrocarbon solvent is n-heptane.

20. A process for preparation of form F of Cyantraniliprole comprising slurring form O of Cyantraniliprole with an aromatic solvent, followed by filtering and drying.

21. The process according to claim 20, wherein the aromatic solvent is toluene.

22. An agrochemical composition comprising a crystalline form according to any one of claims 1-9.

23. Use of a crystalline form according to any one of claims 1-9 in the preparation of an agrochemical composition and / or formulation.

24. An agrochemical formulation comprising a crystalline form according to any one of claims 1-9 or an agrochemical composition of claim 22, and at least one agrochemically acceptable excipient.

25. The agrochemical formulation according to claim 24 further comprising at least one surfactant, solid diluent, liquid diluent, or a combination thereof.

26. A crystalline form according to any one of claims 1-9, an agrochemical composition according to claim 22, or an agrochemical formulation according to claim 24, for use in controlling invertebrate pests in both agronomic and non-agronomic environments.

27. Use of any of a crystalline form according to any one of claims 1-9 for preparing any other crystalline form of Cyantraniliprole.

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